Thermal reactor fuels solvent extraction

When more them one solute is involved in the consideration of the process design, the situation becomes much more complex since the extraction behaviours of the different solutes will usually be interdependent. In the case of irradiated thermal reactor fuels the solvent extraction process will be dealing with uranium containing up to ca. 4% of fission products and other actinides. These will have only a minor effect on uranium distribution so that a single-solute model may be adequate for process design. However, in some cases nitric acid extraction may compete with U02 extraction and a two-solute model may be needed. In the case of breeder reactor fuels the uranium may contain perhaps 20% of plutonium or thorium. Neptunium or protactinium levels in such fuels may also not be negligible and, under these circumstances, the single-solute... 

Solvent extraction processes (i) Thermal reactor fuels... 

There are two breeder reactor fuel cycles. One involves the irradiation of U/ Pu oxide fuel with fast neutrons and is at the prototype stage of development. The other involves the irradiation of Th/ U oxide fuel with thermal neutrons and is at the experimental stage. Fuel from the U/ Pu cycle may be reprocessed using Purex technology adapted to accommodate the significant proportion of plutonium present in the fuel. Increased americium and neptunium levels will also arise compared with thermal reactor fuel. The Th/ U fuel may also be reprocessed using solvent extraction with TBP in the Thorex (Thorium Recovery by Extraction) process. In this case the extraction chemistry must also take account of the presence of Pa arising as shown in Scheme 2. 

The uranium and thorium ore concentrates received by fuel fabrication plants still contain a variety of impurities, some of which may be quite effective neutron absorbers. Such impurities must be almost completely removed if they are not seriously to impair reactor performance. The thermal neutron capture cross sections of the more important contaminants, along with some typical maximum concentrations acceptable for fuel fabrication, are given in Table 9. The removal of these unwanted elements may be effected either by precipitation and fractional crystallization methods, or by solvent extraction. The former methods have been historically important but have now been superseded by solvent extraction with TBP. The thorium or uranium salts so produced are then of sufficient purity to be accepted for fuel preparation or uranium enrichment. Solvent extraction by TBP also forms the basis of the Purex process for separating uranium and plutonium, and the Thorex process for separating uranium and thorium, in irradiated fuels. These processes and the principles of solvent extraction are described in more detail in Section 65.2.4, but the chemistry of U022+ and Th4+ extraction by TBP is considered here. 

Solvent extraction can be carried out in pulsated extraction columns, in mixer-settlers or in centrifuge extractors. Organic compounds such as esters of phosphoric acid, ketones, ethers or long-chain amines are applied as extractants for U and Pu. Some extraction procedures are listed in Table 11.11. The Purex process has found wide application because it may be applied for various kinds of fuel, including that from fast breeder reactors. The Thorex process is a modification of the Purex process and has been developed for reprocessing of fuel from thermal breeders. 

Most LWR fuel rod cladding is made of Zircaloy (and its derivatives), which is an alloy of primarily zirconium and tin. Other alloying elements include niobium, iron, chromium, and nickel. Zircaloy was chosen because it has a very low cross section for thermal neutrons. Naturally occurring zirconium contains about l%-5% hafnium. The hafnium must be removed because it has a very high thermal neutron cross section and is often used in making control rods for reactors. The separation process used in the United States is a liquid-liquid extraction process. It is based on the difference in solubility of the metal thiocyanates in methyl isobutyl ketone. In Europe, a process known as extractive distillation is used to purify zirconium. This method employs a separation solvent that interacts differently with the zirconium and hafnium, causing their relative volatilities to change. This enables them to be separated by a normal distillation process. The separated zirconium is then alloyed with the required constituents. 

---